CN117120365A - Electrostatic dissipative polyamide compositions and articles comprising the same - Google Patents
Electrostatic dissipative polyamide compositions and articles comprising the same Download PDFInfo
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- CN117120365A CN117120365A CN202280025091.7A CN202280025091A CN117120365A CN 117120365 A CN117120365 A CN 117120365A CN 202280025091 A CN202280025091 A CN 202280025091A CN 117120365 A CN117120365 A CN 117120365A
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- 229920002647 polyamide Polymers 0.000 title claims abstract description 252
- 239000004952 Polyamide Substances 0.000 title claims abstract description 237
- 239000000203 mixture Substances 0.000 title claims abstract description 225
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- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 75
- 239000004917 carbon fiber Substances 0.000 claims abstract description 75
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 73
- 239000000945 filler Substances 0.000 claims abstract description 63
- 229920000642 polymer Polymers 0.000 claims abstract description 61
- 239000004020 conductor Substances 0.000 claims abstract description 50
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 39
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 38
- 230000003068 static effect Effects 0.000 claims abstract description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 45
- 238000000465 moulding Methods 0.000 claims description 42
- 239000000835 fiber Substances 0.000 claims description 37
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 37
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- 239000012744 reinforcing agent Substances 0.000 claims description 25
- 239000000654 additive Substances 0.000 claims description 23
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- 238000000034 method Methods 0.000 claims description 23
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- 239000002048 multi walled nanotube Substances 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
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- 229920006883 PAMXD6 Polymers 0.000 claims description 7
- 239000000049 pigment Substances 0.000 claims description 7
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- 229920006115 poly(dodecamethylene terephthalamide) Polymers 0.000 claims description 3
- 229920006139 poly(hexamethylene adipamide-co-hexamethylene terephthalamide) Polymers 0.000 claims description 3
- 229920006131 poly(hexamethylene isophthalamide-co-terephthalamide) Polymers 0.000 claims description 3
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 claims description 3
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims 1
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- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
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- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000000378 calcium silicate Substances 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 2
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- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
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- 239000011777 magnesium Substances 0.000 description 2
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 235000003930 Aegle marmelos Nutrition 0.000 description 1
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- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
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- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
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- YEESUBCSWGVPCE-UHFFFAOYSA-N azanylidyneoxidanium iron(2+) pentacyanide Chemical compound [Fe++].[C-]#N.[C-]#N.[C-]#N.[C-]#N.[C-]#N.N#[O+] YEESUBCSWGVPCE-UHFFFAOYSA-N 0.000 description 1
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Abstract
Described herein are polyamide compositions and molded articles, such as mobile electronic device parts, comprising such polyamide compositions. The polyamide composition comprises: a polyamide polymer; a conductive material comprising carbon fibers, carbon nanotubes, or any combination thereof; and a glass filler having a three-dimensional structure characterized by an average length of at most 500 micrometers, the glass filler comprising at least 20wt% glass flakes. The polyamide composition and the molded article exhibit nearly isotropic mold shrinkage, low warpage, and nearly isotropic CLTE (coefficient of linear thermal expansion), and are static dissipative (ESD).
Description
Cross Reference to Related Applications
The present application claims priority from U.S. provisional application No. 63/171216, filed on 6 at 4 at 2021, and from european patent application No. 21189881.6, filed on 5 at 8 at 2021, the disclosures of which are incorporated herein by reference in their entireties for all purposes.
Technical Field
The present application relates to static dissipative polyamide compositions and also articles, such as molded articles, in particular mobile electronic device parts, comprising such polymer compositions or made from such polymer compositions.
Background
Semi-crystalline polyamides have good mechanical properties and processability, making them well suited for a variety of applications requiring good mechanical properties. Polyamide molded articles are widely used in engineering fields, particularly parts for electronic parts and automotive fields. Due to the need for reduced weight but high mechanical strength molded articles, these articles are often reinforced with fillers, particularly fibrous fillers. Polyphthalamides are of particular interest for their high temperature properties, which result from their high glass transition temperature Tg and high melting temperature Tm.
However, semi-crystalline polyamides exhibit anisotropic molding shrinkage due to crystallization, and fibrous reinforcing fillers (like glass fibers) enhance this effect. In addition, dimensional stability, such as the coefficient of linear thermal expansion "CLTE", or hygroscopic expansion, is also anisotropic, caused by the semi-crystalline polymer morphology and the high aspect ratio of the reinforcing filler.
Polyamide is an insulating material as most plastic resins. In fact, plastic resins are often considered for use as electrically insulating materials, as they are typically not readily conductive to electrical current and are often quite inexpensive relative to other known insulating materials. Many known plastics are durable and heat resistant enough to provide at least some electrical insulation utility, but many such plastics are problematic due to the build up of electrostatic charges on the surface of the material.
Such surface charge accumulation may be undesirable for various reasons. Such materials sometimes discharge very rapidly and this can damage electronic components or cause fires or explosions, depending on the circumstances. For those cases where the material is used, abrupt electrostatic discharge can also be annoying.
Even in cases where sudden electrostatic discharge is not an issue, dust will typically be attracted to the electrostatically charged material and will accumulate thereon. Furthermore, static charges may interfere with sensitive electronic components or devices, etc.
Resistivity may be defined as relating to surface resistivity and volume resistivity. If the volume resistivity is within the appropriate range, an alternative path is provided through which charge can dissipate (typically along the surface). In fact, surface resistivity is typically the primary focus of electrostatic dissipative ("ESD") polymeric materials.
Surface resistivity is a measure of resistance (typically measured in ohms/square or "Ω/sq") taken at room temperature at the surface of a material. At a surface resistivity of less than or equal to about 10 5 In the case of Ω/sq, the surface of the composition has very little insulating ability and is generally considered to be conductive. Such compositions are typically polymeric materials with poor static dissipation because the bleed rate is too high.
At a surface resistivity of greater than 10 12 In the case of Ω/sq, the surface of the composition is generally considered as an insulator. In some applications, such compositions are also materials with poor static dissipation, as the surface does not have the necessary amount of conductivity to dissipate static charge. Typically, the surface resistivity is about 10 5 To 10 12 In the case of Ω/sq, any of the contact surfacesWhich charge will be easily dissipated or "decayed". Additional information concerning the evaluation of surface and volume resistivity can be found in U.S. standard test method D257. The polymer composition may be made conductive by the addition of a conductive additive. These conductive additives may include carbon fibers, carbon black, carbon nanotubes, graphene, or graphite. These conductive additives may also include surfactants, salts, conductive organic polymers, and conductive inorganic polymers.
Disclosure of Invention
It is therefore an object of the present invention to provide a polyamide composition which is used for the manufacture of polyamide-based articles, preferably molded articles, having electrostatic dissipative (ESD) properties and suitable dimensional stability. This combination of characteristics makes such articles well suited for electronic applications and in particular for mobile electronic device components having tight dimensional tolerances and requiring ESD characteristics for optimal function.
The present invention solves the problems of anisotropic molding shrinkage and dimensional variation (low warpage) in polyamide-based molded articles (such as components of mobile electronic devices) with very tight dimensional tolerances. "warpage" means the deformation of a molded part in one or more directions, which may be caused by anisotropic shrinkage of the resin during molding.
The present invention also solves the problem of poor static dissipation in polyamide-based articles or devices that accumulate static charges generated during their operation in a manner that promotes slow dissipation of these static charges. Without conductive material, the polyamide-based article or device would be insulating and no charge dissipation would occur. On the other hand, in the case of too much conductive material, the polyamide-based article or device has too low a resistivity (too conductive), resulting in grounding of the article or device, which may inhibit its performance.
A first aspect of the invention relates to a polyamide composition comprising a polyamide polymer, an electrically conductive material and a glass filler having a three-dimensional structure characterized by an average length of at most 500 micrometers.
The polyamide composition comprises:
At least 20 weight percent (wt%) of a polyamide polymer,
from greater than 1wt% and up to 20wt% of a conductive material comprising carbon fibers, carbon nanotubes, or any combination thereof, and
from 20 to 60% by weight of a glass filler having a three-dimensional structure characterized by an average length of at most 500 micrometers, said glass filler comprising at least 20% by weight of glass flakes,
wherein the wt% is based on the total weight of the polyamide composition.
A particular polyamide composition comprises:
at least 20 weight percent (wt%) of a polyamide polymer,
from greater than 1wt% and up to 20wt% of a carbon-based conductive material comprising carbon fibers, carbon nanotubes, or any combination thereof, and
from 30 to 55% by weight of a glass filler consisting of glass flakes,
wherein the wt% is based on the total weight of the polyamide composition.
The polyamide composition may further comprise optional reinforcing agents other than glass fillers, and/or optional additives, for example, heat stabilizers, lubricants, impact modifiers, UV stabilizers, pigments, and the like.
A second aspect of the invention relates to a process for manufacturing a polyamide composition according to the invention, comprising melt blending a polyamide polymer, an electrically conductive material, a glass filler, an optional reinforcing agent different from the glass filler, and an optional additive (e.g., a heat stabilizer, a lubricant, an impact modifier, a UV stabilizer, a pigment, etc.).
A third aspect of the invention relates to a molded article comprising or made from the polyamide composition according to the invention.
A fourth aspect of the invention relates to an electronic device component, preferably a mobile electronic device component, comprising or made of the polyamide composition according to the invention.
A fifth aspect of the invention relates to the use of a polyamide composition according to the invention for the manufacture of a molded article, such as a mobile electronic device component.
Another aspect of the invention relates to a method for reducing the surface or volume resistivity and also reducing the molding shrinkage and/or warpage of a polyamide-based molded article, the method comprising blending a polyamide polymer with a conductive material, a glass filler and optionally additives to form a molding composition, and then subjecting the molding composition to molding, preferably injection molding, to form the molded article.
Various aspects, advantages, and features of the present invention will be more readily understood and appreciated by reference to the following detailed description and examples.
Definition of the definition
In this descriptive specification, some terms are intended to have the following meanings.
As used herein, polyamides are generally obtained by polycondensation between at least one aromatic or aliphatic saturated diacid and at least one aliphatic saturated or aromatic primary diamine, lactam, amino acid or a mixture of these different monomers.
As used herein, polyphthalamides (PPAs) are generally obtained by polycondensation between at least one diacid and at least one diamine, wherein at least 55 mole percent of the diacid moieties of the repeat units in the polymer chain are terephthalic acid and/or isophthalic acid, and wherein the diamine is aliphatic.
As used herein, an aliphatic polyamide polymer comprises at least 50 mole% of recurring units having amide linkages (-NH-CO-) and which are free of any aromatic groups. In other words, the diacid moieties of the repeat units of the polyamide formed by polycondensation do not contain any aromatic groups with either the diamine, lactam or amino acid moieties.
As used herein, a "semi-crystalline" polyamide includes a heat of fusion ("Δh") of at least 5 joules/gram (J/g) measured using differential scanning calorimetry at a heating rate of 20 ℃/min f "). Similarly, as used herein, amorphous polyamide includes an addition at 20 ℃/minΔH of less than 5J/g measured using differential scanning calorimetry at a thermal rate f 。ΔH f Can be measured according to ASTM D3418. In some embodiments, ΔH f Is at least 20J/g, or at least 30J/g, or at least 40J/g.
As used herein, unless otherwise indicated, when referring to the "glass transition temperature" Tg and "melting temperature" Tm of the polyamide in the polyamide composition, tg and Tm are preferably measured according to ASTM D3418.
The term "nano" as used herein in association with a three-dimensional structure such as a tube, sheet, flake, disk, sphere, or any other 3-D structure refers to a structure having at least one dimension less than about 0.1 microns (< 100 nanometers) and an aspect ratio from about 50:1 to about 5000:1 from the longest dimension to the shortest dimension. The size of the nano 3-D structure may be determined by dynamic light scattering (DSL) and/or by direct measurement of a micrograph obtained by Scanning Electron Microscopy (SEM).
In this specification, selecting an element from a set of elements also explicitly describes:
selecting two or several elements from the group,
-selecting an element from a subset of elements consisting of the set of elements from which one or more elements have been removed.
In the following paragraphs of this specification, even any description described with respect to specific embodiments may be applicable to and interchangeable with other embodiments of the present disclosure. Each embodiment so defined may be combined with another embodiment unless otherwise indicated or clearly incompatible. In addition, it is to be understood that elements and/or features of a composition, component, or article, process, method, or use described in this specification may be combined in all possible ways with other elements and/or features of the composition, component, or article, process, method, or use, either explicitly or implicitly, without departing from the scope of this specification.
In this specification, the description of a series of values for a variable defined by a lower limit, or an upper limit, or both, also includes embodiments in which the variable is correspondingly selected within the numerical range: the lower limit is not included, or the upper limit is not included, or both the lower limit and the upper limit are not included. Any recitation of numerical ranges by endpoints herein includes all numbers subsumed within that recited range, as well as the endpoints and equivalents of that range.
The term "comprising" includes "consisting essentially of" (consisting essentially of or consist essentially of) and "consisting of" (consisiting of or consisiting of). As used herein, "consisting essentially of" with respect to a composition means that the content of one or more components not explicitly listed in the composition is less than 1wt%, or less than 0.5wt%, or less than 0.1wt%, or less than 0.05wt%, or less than 0.01wt%, based on the total weight of the composition.
As used herein, the singular "a", "an", or "one" include plural referents unless the content clearly dictates otherwise.
Detailed Description
When the polyamide composition according to the invention comprises a polyamide polymer, an electrically conductive material, a glass filler, one or more optional reinforcing agents different from the glass filler, and optional additives, it has surprisingly been found that the resulting polyamide composition results in a polyamide-based molded article having static dissipative properties, improved dimensional stability (CLTE) and improved shrinkage and/or warpage properties, while exhibiting suitable mechanical properties.
Molded articles containing such polyamide compositions according to the invention or made therefrom exhibit a nearly isotropic molding shrinkage and/or low warpage and a nearly isotropic CLTE (coefficient of linear thermal expansion). In addition, the volume resistivity is such that a molded article containing such polyamide composition according to the invention or made therefrom is static dissipative (ESD). This combination makes the polyamide composition according to the invention very suitable for electronic applications with tight dimensional tolerances and which require ESD properties for optimal function. Preferably, molded articles containing or made from such polyamide compositions according to the invention are electronic device parts.
In some embodiments, the polyamide-based molded article or electronic device component has a weight ratio of at least 1.10 +5 Omega cm, or at least 1.5.10 +5 Omega cm, and/or up to 5.10 +12 Omega cm, or at most 3.10 +12 Omega cm, or at most 1.10 +12 Volume resistivity of Ω. cm (measured according to ASTM D257). In some embodiments, the polyamide-based molded article or electronic device component has a weight ratio of from 1.10 +5 Omega cm to 5.10 +12 Volume resistivity of Ω·cm. Thus, by selecting a conductive material having a specific volume resistivity and varying the content of the conductive material in the polyamide composition used to make the molded article, the volume resistivity is adjustable within about at least 7 orders of magnitude.
In some embodiments, the polyamide-based molded article or electronic device component according to the present invention has a molding shrinkage (%) in the transverse direction of at most 0.5%, or at most 0.47%, or at most 0.45%, or at most 0.44%, determined according to ISO 294 (ASTM D955).
In some embodiments, a polyamide-based molded article or electronic device component according to the present invention has a ratio of mold shrinkage in the flow direction to mold shrinkage in the transverse direction of greater than 32%, or greater than 35%, or greater than 40%, or greater than 45%, or greater than 50%, or greater than 55%, or greater than 60%, wherein the mold shrinkage in the flow direction and in the transverse direction (in%) is determined according to ISO 294 (ASTM D955).
In some embodiments, the polyamide-based molded article or electronic device component according to the present invention has a warpage of at most 0.5, or at most 0.4, or at most 0.3, or at most 0.2, or at most 0.18. Warpage is the absolute value of the percent shrinkage in the transverse direction minus the percent shrinkage in the flow direction of a molded article or electronic device component comprising the polyamide composition, both percent shrinkage preferably determined according to ASTM D955.
In some embodiments, a polyamide-based molded article or electronic device component according to the present invention produced by molding a polyamide composition comprising from greater than 1wt% to 20wt% of at least one polyamide polymer, from greater than 1wt% to 20wt% of a conductive material, at least 20wt% of a glass flake as at least one glass filler, optionally one or more reinforcing agents, and optionally additives (e.g., heat stabilizers, lubricants, impact modifiers, UV stabilizers, pigments, etc.), has a lower degree of warpage (in%) than a similar composition in which the glass flakes are replaced with glass fibers.
In some embodiments, the polyamide composition according to the invention does not comprise more than 5wt%, preferably does not comprise more than 2wt%, more preferably does not comprise more than 1wt% of polymers other than one or more polyamide polymers.
In some embodiments, a polyamide composition according to the present invention consists essentially of a polyamide polymer, a conductive material, a glass filler, optionally one or more reinforcing agents other than glass filler, and optionally additives (e.g., heat stabilizers, lubricants, impact modifiers, UV stabilizers, pigments, etc.), as described herein. The term "consisting essentially of" with respect to a polyamide composition means that the content of one or more components not explicitly described in the composition is less than 1wt%, or less than 0.5wt%, or less than 0.1wt%, or less than 0.05wt%, or less than 0.01wt%, based on the total weight of the polyamide composition.
Polyamide polymers
The polyamide composition comprises at least 20wt% of at least one polyamide polymer, based on the total weight of the polyamide composition.
The polyamide polymer in the polyamide composition may comprise a semiaromatic polyamide. In such cases, the polyamide polymer in the polyamide composition may comprise a semiaromatic polyamide selected from the group consisting of: PA10T/10I; PA10T; PA6T/6I; PA6T; PA9T; PA12T; PA10T/66; PA6T/66; PA6, I; PA12I; PAMXD6; PAPXD10; and any combination thereof.
The polyamide polymer in the polyamide composition may comprise, or consist essentially of, at least one polyphthalamide. In such cases, the polyamide polymer in the polyamide composition may comprise, or consist essentially of, at least one polyphthalamide selected from the group consisting of: PA10T/10I; PA10T; PA6T/6I; PA6T; PA9T; PA12T; PA10T/66; PA6T/66; PA6, I; PA12I; and any combination thereof.
The polyamide polymer in the polyamide composition may comprise an aliphatic polyamide. In such cases, the polyamide polymer in the polyamide composition may be selected from the group consisting of: PA610; PA612; PA1010; PA12; PA510; PA66; PA1012; and any combination thereof.
The at least one polyamide polymer is present in the polyamide composition in an amount of at least 20wt%, or at least 25wt%, or at least 30wt%, based on the total weight of the polyamide composition.
The polyamide polymer may be present in the polyamide composition in an amount of up to 89.9wt%, or up to 85wt%, or up to 80wt%, or up to 75wt%, or up to 70wt%, or up to 65wt%, based on the total weight of the polyamide composition.
In some embodiments, the polyamide composition may include a variety of different polyamide polymers according to the description above. In such cases, the total content of the different polyamide polymers is within the ranges described above. A specific example of such an embodiment is when the polyamide polymer comprises, or consists essentially of, a combination of PA6,10 and PAMDX 6. Another example of such an embodiment is when the polyamide polymer comprises, or consists essentially of, a combination of PA10T/10I and PAMDX 6. The PAMXD6 polymer is a polymer made from adipic acid and m-xylylenediamine (notably as a polymer from the american sorv specialty polymers company of liability (Solvay Specialty Polymers u.s.a., l.l.c.))The polyarylamides are commercially available).
One of the polyamide polymers (e.g., PAMXD6 polymer) in the polyamide composition may be a polymeric carrier to form a masterbatch into which the additives or/and conductive material are mixed prior to making the polyamide composition. In this case, the weight content (wt%) of such polyamide (e.g., PAMXD 6) used as a masterbatch polymer carrier should be less than the weight content (wt%) of the other polyamide(s), each wt% of the other polyamide(s) based on the total weight of the polyamide composition.
The polyamide polymer may comprise at least one semiaromatic polyamide and at least one aliphatic polyamide. In such cases, the weight ratio of the at least one semi-aromatic polyamide based on the combined weight of the different polyamides in the polyamide composition may be lower than the weight ratio of the at least one aliphatic polyamide based on the combined weight of the different polyamides in the polyamide composition.
In some embodiments, the polyamide composition may not include an aromatic polyamide.
In alternative embodiments, the polyamide composition may not comprise an aliphatic polyamide.
The polyamide composition may not include a polyamide made from a single monomer, such as PA6.
The polyamide composition may not include a polyamide made from two monomers containing 6 carbons or less, such as PA66.
The polyamide polymer is preferably a semi-crystalline polyamide.
At least a portion of the polyamide polymer in the polyamide composition may be biobased.
The polyamide composition may comprise any polyamide having a Tg of less than 80 ℃ and/or a Tm of less than 250 ℃.
Alternatively, the polyamide composition may comprise a polyamide polymer having a Tg of at least 80 ℃, at least 95 ℃, or at least 100 ℃.
The polyamide polymer may have a Tg of no more than 200 ℃, no more than 180 ℃, no more than 160 ℃, no more than 150 ℃, no more than 140 ℃, or no more than 135 ℃. In this case, the polyamide polymer may have a Tg of from 80 ℃ to 150 ℃, from 100 ℃ to 140 ℃, or from 100 ℃ to 135 ℃.
The polyamide polymer may have a melting temperature Tm of at least 230 ℃, at least 260 ℃, or at least 265 ℃. The polyamide polymer may have a Tm of no more than 360 ℃, no more than 350 ℃, or no more than 340 ℃, or no more than 330 ℃. In this case, the polyamide polymer may have a Tm of from 230 ℃ to 360 ℃, from 260 ℃ to 350 ℃, or from 265 ℃ to 330 ℃. Tg and Tm can be measured according to ASTM D3418.
Conductive material
The polyamide composition further comprises more than 1wt% and up to 20wt% of at least one electrically conductive material comprising carbon fibers, carbon nanotubes, or any combination thereof. The electrically conductive material provides improved ESD of the polyamide composition and articles or devices made from or incorporating the polyamide composition therein.
The conductive material preferably has a dielectric constant of less than 2.10 -2 Omega cm, or at most 1.10 -2 Omega cm, or at most 5.10 -3 Omega cm, or at most 3.10 -3 Omega cm, or at most 2.10 -3 Volume resistivity of Ω·cm. The conductive material preferably has a dielectric constant of at least 1.10 -4 Volume resistivity of Ω·cm. The conductive material may have a composition of 1.10 -4 Omega cm to 20.10 -4 Volume resistivity of Ω·cm.
The conductive material may have at least 0.1m as measured by a standard Brunauer-Emmett-Teller (Brunauer-Emmett-Teller) method of measurement (BET) 2 /g, preferably 10m 2 /g or higher, e.g. from about 10m 2 /g to about 500m 2 Specific Surface Area (SSA) per gram. For example, the BET measurement method of Micro-metrics TriStar II having a standard nitrogen system may be used.
The conductive material may comprise, or consist essentially of, a carbon-based structure selected from the group consisting of: metallized carbon fibers, chopped carbon fibers, milled/chopped carbon fibers in particles, carbon nanotubes such as single wall carbon nanotubes ("SWCNTs"), double wall carbon nanotubes ("DWCNTs"), multi wall carbon nanotubes ("MWCNTs") (which consist of nested SWCNTs), and any mixtures thereof. The conductive material preferably comprises, or consists essentially of, a carbon-based structure selected from the group consisting of: chopped carbon fibers, milled/chopped carbon fibers in particulate form, carbon nanotubes, and any mixtures thereof.
Preferred carbon fibers include, but are not limited to, chopped carbon fibers, milled carbon fibers, and/or milled/chopped carbon fibers in particulate form.
Preferred chopped carbon fibers compatible with polyamides are commercially available from Procotex as CF.OS.U1-6 mm, CF.OS.U2-6 mm, CF.OS.A-6mm, CF.OS.I-6mm having an average filament diameter of 7 microns, an average length of 6mm and 15.10 -4 Omega cm to 20.10 -4 Volume resistivity of Ω·cm.
The preferred milled carbon fibers are commercially available from Procotex as CF.LS-MLD80 to CF.LS-MLD250, having an average filament diameter of 7 microns, a median length of 80-250 microns, and 15.10 -4 Omega cm to 20.10 -4 Volume resistivity of Ω·cm.
Carbon nanotubes are examples of nano-or molecular-sized conductive materials. Preferably, the carbon nanotubes are MWCNTs. Carbon nanotubes and ropes of carbon nanotubes such as ropes of carbon nanotubes (e.g., ropes of SWNTs or MWNTs and SWNTs or MWNTs) exhibit high mechanical strength, electrical conductivity, and high thermal conductivity.
Suitable multi-wall CNTs (MWCNTs) include those having purities as low as 90% C purityNC7000MWCNT grade or C purity with a C purity of more than 95%>NC3100MWCNT grade, both from Nanocyl (belgium). / >NC7000 MWCNTs with an average diameter of 9.5 nm, an average length of 1.5 μm, 250-300m 2 BET surface area per gram and 1.10 -4 Volume resistivity of Ω·cm. Other suitable sources of carbon nanotubes are +.>Multiwall carbon nanotubes. These MWCNTs may have an outer diameter of about 10 nanometers and a length exceeding 10 microns.
The carbon nanotubes may have an average aspect ratio defined as length divided by diameter of 100 or more. The carbon nanotubes may have an average aspect ratio of 1000 or more. The carbon nanotubes may have an average diameter from 1 nanometer (nm) to 3.5nm or 4nm (ropes). The carbon nanotubes may have an average length of at least 1 μm.
The conductive material may further comprise one or more other three-dimensional structures selected from the group consisting of: fibers, flakes, powders, microspheres, nanoparticles, nanofibers, nanoflakes (nano-discs), nanoropes, nanoribbons, nanofibres, nanoneedles, nanoplatelets (nano-sheets), nanorods, carbon nanocones, carbon nanorolls (carbon nano-scroll), nanoplatelets (nano-plates), nanodots, dendrites, disks, or any other three-dimensional body, alone or in combination.
Alternatively or additionally, the conductive material may further comprise at least one material selected from the group consisting of: metal flakes, metal powders, metallized glass spheres, metallized glass fibers, metal fibers, metallized whiskers, inherently conductive polymers, and/or graphite fibrils.
The conductive material is preferably composed of only one or more carbon-based structures. The carbon-based structure typically comprises at least 90wt% carbon. Commercially available technical grade carbon-based structures or nanostructures with 90% -95% C purity can be directly dispersed in polyamide polymers without pretreatment.
In addition to carbon fibers and/or carbon nanotubes, the conductive material may further comprise a carbon-based structure selected from the group consisting of: carbon nanofibers, carbon nanoflakes, carbon nanoropes, carbon nanoribbons, carbon nanofibers, carbon nanoneedles, carbon nanoplatelets, carbon nanorods, carbon nanocones, carbon nanorolls, carbon nano-ohms (carbon nano-ohms), conductive carbon black powder, graphite fibrils, graphite nanoplatelets, nanodots, graphene, or any combination of two or more thereof.
The conductive material preferably comprises, or consists of:
-a carbon-based structure selected from the group consisting of: carbon fibers, carbon Nanotubes (CNTs) such as SWCNTs, DWCNTs, and MWCNTs, and any combination thereof, and
-optionally ropes of carbon nanotubes, carbon black powder, or any combination thereof.
The conductive material content in the polyamide composition is more than 1wt%, or at least 1.5wt% and at most 20wt% based on the total weight of the polyamide composition.
When the conductive material comprises carbon fibers, the carbon fiber content in the polyamide composition is at least 6wt%, or at least 8wt%, or at least 10wt%, based on the total weight of the polyamide composition. In such cases, the carbon fiber content is at most 20wt%, or at most 17wt%, or at most 15wt%, based on the total weight of the polyamide composition. The carbon fiber content may be from 6wt% to 20wt%, or from 8wt% to 20wt%, or from 10wt% to 20wt%, or from 6wt% to 15wt%, or from 8wt% to 15wt%, or from 10wt% to 20wt%, or from 10wt% to 15wt%, based on the total weight of the polyamide composition.
When the conductive material comprises carbon nanotubes, the carbon nanotubes are present in the polyamide composition in an amount of greater than 1wt%, or at least 1.5wt%, based on the total weight of the polyamide composition. In such cases, the content of Carbon Nanotubes (CNT) is at most 8wt%, or at most 7wt%, or at most 6wt%, or at most 5wt%, or at most 4wt%, or at most 3wt%, based on the total weight of the polyamide composition. The carbon nanotubes when present in the polyamide composition may be present in an amount of from greater than 1wt% and up to 8wt%, or from greater than 1wt% and up to 5wt%, or from greater than 1wt% and up to 4wt%, or from greater than 1wt% and up to 3wt%, or from 1.5wt% to 8wt%, or from 1.5wt% to 5wt%, or from 1.5wt% to 3wt%, based on the total weight of the polyamide composition.
When the conductive material further comprises carbon black powder, the carbon black powder content in the polyamide composition may be from 0.1wt%, or at least 0.5wt%, or at least 1wt%, based on the total weight of the polyamide composition. In such cases, the carbon black powder content in the polyamide composition is up to 10wt%, based on the total weight of the polyamide composition.
When the conductive material further comprises other carbon-based nanostructures (in addition to carbon nanotubes), their content in the polyamide composition may be from 0.1wt% to 5wt%, or from 0.1wt% to 4wt%, or from 0.1wt% to 3wt%, or from 0.5wt% to 5wt%, or from 0.5wt% to 4wt%, or from 0.5wt% to 3wt%, or from 1wt% to 8wt%, or from 1wt% to 5wt%, or from 1wt% to 4wt%, or from 1wt% to 3wt%, or from 1.5wt% to 8wt%, or from 1.5wt% to 5wt%, or from 1.5wt% to 3wt%, based on the total weight of the polyamide composition.
Glass filler
The polyamide composition further comprises from 20 to 60 weight percent of at least one glass filler having a three-dimensional structure characterized by an average length of at most 500 micrometers, or at most 450 micrometers, or at most 400 micrometers, or at most 350 micrometers, or at most 200 micrometers, or at most 250 micrometers. For glass fillers having a three-dimensional structure, the "length" is considered to be its longest dimension. The wt% is based on the total weight of the polyamide composition.
The glass filler is preferably an electrically insulating filler, typically having a weight of greater than 10 +12 Omega cm or greater than 5.10 +12 Volume resistivity of Ω·cm.
The glass filler is preferably non-fibrous. "non-fibrous" fillers are considered herein to have a three-dimensional structure (having a length, a width, and a thickness), where both the length and the width are significantly greater than their thickness. Typically, such glass fillers having a three-dimensional structure have an aspect ratio defined as the average length divided by the maximum of the average width and average thickness of at most 3, or at most 2.5, or at most 2, or at most 1.5.
The dimensions (length, width, thickness) of the three-dimensional structure can be determined by direct measurement on a micrograph obtained by Scanning Electron Microscopy (SEM).
The average size (i.e., length, width, and thickness) of the three-dimensional structure of the glass filler may be taken as the average length of the glass filler prior to incorporation into the polyamide composition, or may be taken as the average size of the glass filler in the polyamide composition.
Glass fillers are silica-based glass compounds containing several metal oxides that can be tailored to produce different types of glass. The primary oxide is silica in the form of silica sand; other oxides (such as calcium, sodium and aluminum) are incorporated to lower the melting temperature and to hinder crystallization. Any glass type may be used in the glass filler, such as A, C, D, E, M, S, R, T glass or mixtures thereof, preferably C or E glass. The C glass contains an alkaline component and has high acid resistance. The E-glass contains almost no alkali, and thus it has high stability in the resin and no conductivity.
The glass filler comprises at least 20wt% glass flakes, based on the total weight of the polyamide composition.
The glass filler may consist essentially of glass flakes such that the polyamide composition comprises from 20 to 60wt% glass flakes, preferably from 30 to 55wt% glass flakes, based on the total weight of the polyamide composition.
The glass flakes may be glass flakes having C or E glass. Suitable glass flakes having E or C glass are those from Nitro Japan (NSG) as a materialAre commercially available. The E-glass flakes are particularly effective in preventing warpage and improving dimensional accuracy of precision parts made of thermoplastic polymers. />Glass flakes are also commercially available from japan plate Nitroprusside (NSG), having an average thickness of 0.4 to 1 micron, suitable for use in fine and thin molded products. The glass flakes may be particulate. For example, have E glass +.>The particulate glass flakes were obtainable from Nitro Kagaku Kogyo (NSG)Commercially available.
The glass flakes may have an average thickness of from 0.4 microns to 10 microns. In some embodiments, the glass flakes may have an average thickness of from 0.4 microns to 2 microns, or to 1 micron.
The glass filler may further comprise chopped glass fibers provided that the average length thereof is at most 500 micrometers, or at most 450 micrometers, or at most 400 micrometers, or at most 350 micrometers, or at most 200 micrometers, or at most 250 micrometers.
Where the glass filler comprises both glass flakes and chopped glass fibers (both characterized by an average length of at most 500 micrometers, or at most 450 micrometers, or at most 400 micrometers, or at most 350 micrometers, or at most 200 micrometers, or at most 250 micrometers), their combined amount is not more than 60 weight percent based on the total weight of the polyamide composition.
Furthermore, when the glass filler comprises both glass flakes and chopped glass fibers, the glass flakes preferably comprise a weight fraction (in wt%) of greater than 50wt%, or greater than 60wt%, or greater than 70wt%, or greater than 80wt% of the glass filler (the weight fraction (in wt%) being based on the combined weight of the glass flakes and chopped glass fibers). As an example, if the glass flake content in the polyamide composition is 30wt%, the chopped glass fiber content should be less than 30wt% (based on the total weight of the polyamide composition).
When present in the glass filler, the chopped glass fibers may generally have a thickness of from 5 to 20 μm, preferably from 5 to 15 μm and more preferably from 5 to 10 μm. The chopped glass fibers may have an average length of at least 50 microns, or at least 100 microns, or at least 150 microns, or at least 200 microns, or at least 250 microns. The chopped glass fibers may have an average length of from 100 to 500 micrometers, or from 150 to 450 micrometers.
The chopped glass fibers may have an aspect ratio defined as the maximum of its average length divided by its average width and average thickness of at most 5, or at most 3, or at most 2.5, or at most 2, or at most 1.5.
The morphology of the chopped glass fibers is not particularly limited. Chopped glass fibers may have a circular cross-section ("round glass fibers") or a non-circular cross-section ("flat glass fibers"). Examples of suitable flat glass fibers include, but are not limited to, glass fibers having oval, elliptical, and rectangular cross-sections.
In the case where the glass filler further comprises chopped flat glass fibers, the flat glass fibers have an average width (cross-sectional longest dimension) of at least 15 μm, preferably at least 20 μm, more preferably at least 22 μm, still more preferably at least 25 μm. Additionally or alternatively, in some embodiments, the chopped flat glass fibers have an average width (cross-sectional longest diameter) of at most 40 μm, preferably at most 35 μm, more preferably at most 32 μm, still more preferably at most 30 μm. The chopped flat glass fibers may have an average width (cross-sectional longest diameter) in the range of 15 to 35 μm, preferably 20 to 30 μm and more preferably 25 to 29 μm. The chopped flat glass fibers may have a thickness (cross-sectional shortest diameter) of at least 4 μm, preferably at least 5 μm, more preferably at least 6 μm, still more preferably at least 7 μm. Additionally or alternatively, the chopped flat glass fibers may have a thickness (cross-sectional shortest diameter) of at most 25 μm, preferably at most 20 μm, more preferably at most 17 μm, still more preferably at most 15 μm. The chopped flat glass fibers may have a thickness (cross-sectional shortest diameter) in the range of 5 to 20, preferably 5 to 15, and more preferably 7 to 11 μm.
The chopped flat glass fibers may have a ratio of the width (longest diameter in cross section) to the thickness (shortest diameter in the same cross section) of the glass fibers of at least 2, preferably at least 2.2, more preferably at least 2.4, still more preferably at least 3. Additionally or alternatively, the chopped flat glass fibers may have a ratio of width (longest diameter in cross section) to thickness (shortest diameter in the same cross section) of the glass fibers of at most 8, preferably at most 6, more preferably at most 4. The chopped flat glass fibers may have a ratio of the width (longest diameter in cross section) to the thickness (shortest diameter in the same cross section) of the glass fibers from 2 to 6 and preferably from 2.2 to 4.
The glass filler content in the polyamide composition is at least 20wt%, or at least 25wt%, or at least 30wt%, based on the total weight of the polyamide composition. The glass filler content is at most 60wt%, or at most 55wt%, or at most 50wt%, based on the total weight of the polyamide composition. The glass filler content in the polyamide composition is from 20wt% to 60wt%, or may be from 25wt% to 60wt%, or from 30wt% to 60wt%, or from 20wt% to 55wt%, or from 25wt% to 55wt%, or from 30wt% to 55wt%, or from 20wt% to 50wt%, or from 25wt% to 50wt%, or from 30wt% to 50wt%, based on the total weight of the polyamide composition.
The polyamide composition comprises at least 20wt%, or at least 25wt%, or at least 30wt% of glass flakes, based on the total weight of the polyamide composition. The polyamide composition comprises up to 60wt%, or up to 55wt%, or up to 50wt% of glass flakes, based on the total weight of the polyamide composition.
The glass flake content in the polyamide composition may be from 20wt% to 60wt%, or from 25wt% to 60wt%, or from 30wt% to 60wt%, or from 20wt% to 55wt%, or from 25wt% to 55wt%, or from 30wt% to 55wt%, or from 20wt% to 50wt%, or from 25wt% to 50wt%, or from 30wt% to 50wt%, based on the total weight of the polyamide composition.
Optional reinforcing agent
As described above, the polyamide composition may further comprise at least one optional reinforcing agent other than glass filler.
A large amount of selected reinforcing agents (also referred to as reinforcing fillers) may optionally be added to the polyamide composition according to the invention. They may be selected from fibrous reinforcing agents and particulate reinforcing agents.
The optional reinforcing agent may be selected from mineral fillers (such as talc, mica, kaolin, calcium carbonate, calcium silicate, magnesium carbonate), carbon fibers, synthetic polymer fibers, aromatic polyamide fibers, aluminum fibers, titanium fibers, magnesium fibers, boron carbide fibers, rock wool fibers, steel fibers, wollastonite, glass spheres (e.g., hollow glass microspheres), and glass fibers (other than the glass fillers used in the polyamide composition according to the invention).
The particulate reinforcing agent may be selected from mineral fillers (e.g. talc, mica, kaolin, calcium carbonate, calcium silicate, magnesium carbonate) or glass spheres (e.g. hollow glass microspheres).
Fibrous reinforcing fillers are considered herein to be three-dimensional materials having a length, a width, and a thickness, wherein the average length is significantly greater than both the width and the thickness. Typically, such materials have an aspect ratio defined as the ratio between the average length and the largest of the average width and average thickness of at least 5, at least 10, at least 20, or at least 50.
The optional reinforcing fibers (e.g., glass fibers) may be chopped glass fibers (other than glass fillers) having an average length of greater than 0.5mm, preferably at least 1mm and up to 50mm, or continuous glass fibers. The average length of the optional reinforcing glass fibers may be taken as the average length of the reinforcing glass fibers prior to incorporation into the polyamide composition or may be taken as the average length of the reinforcing fibers in the polyamide composition.
The optional glass fibers may have an average length of from 3mm to 50mm, or from 3mm to 10mm, from 3mm to 8mm, from 3mm to 6mm, or from 3mm to 5 mm. Alternatively, the optional glass fibers may have an average length of from 10mm to 50mm, from 10mm to 45mm, from 10mm to 35mm, from 10mm to 30mm, from 10mm to 25mm, or from 15mm to 25 mm. In such cases, the optional glass fibers may generally have an equivalent diameter from 5 to 20 μm, preferably from 5 to 15 μm and more preferably from 5 to 10 μm.
All glass types may be used, such as A, C, D, E, M, S, R, T glass or any mixture or mixture thereof. E. R, S and T glass fibers are well known in the art. They are notably described in Fiberglass and Glass Technology [ glass fibers and glass technology ]]Wallenberger, frederick t.; bingham, paul A. (editions), 2010, XIV, chapter 5, pages 197-225. R, S and T glass fibers consist essentially of oxides of silicon, aluminum and magnesium. In particular, those glass fibers typically contain 62 to 75wt.% SiO 2 16-28wt.% Al 2 O 3 And 5 to 14wt.% MgO. In addition, R, S and T glass fibers comprise less than 10wt.% CaO.
The optional glass fibers may comprise or consist of high modulus glass fibers. The high modulus glass fiber has an elastic modulus of at least 76GPa, preferably at least 78GPa, more preferably at least 80GPa, and most preferably at least 82GPa as measured according to ASTM D2343. Examples of high modulus glass fibers include, but are not limited to S, R and T glass fibers. A commercially available source of high modulus glass fibers is S-1 and S-2 glass fibers from Taishan corporation (Taishan) and AGY corporation, respectively.
The optional glass fibers may comprise or consist of round glass fibers or flat glass fibers. Examples of suitable flat glass fibers include, but are not limited to, glass fibers having oval, elliptical, and rectangular cross-sections.
When the polyamide composition further comprises flat glass fibers, the flat glass fibers may have a cross-sectional longest diameter of at least 15 μm, preferably at least 20 μm, more preferably at least 22 μm, still more preferably at least 25 μm. Additionally or alternatively, the flat glass fibers may have a cross-sectional longest diameter of at most 40 μm, preferably at most 35 μm, more preferably at most 32 μm, still more preferably at most 30 μm. In some embodiments, the flat glass fibers may have a cross-sectional shortest diameter of at least 4 μm, preferably at least 5 μm, more preferably at least 6 μm, still more preferably at least 7 μm. Additionally or alternatively, the flat glass fibers may have a cross-sectional shortest diameter of at most 25 μm, preferably at most 20 μm, more preferably at most 17 μm, still more preferably at most 15 μm.
The optional flat glass fibers may have a ratio of the longest diameter in a cross section of the glass fibers to the shortest diameter in the same cross section of at least 2, preferably at least 2.2, more preferably at least 2.4, still more preferably at least 3. Additionally or alternatively, the ratio of flat glass fibers may be at most 8, preferably at most 6, more preferably at most 4.
When the optional glass fibers are round glass fibers, the glass fibers can have a ratio of the longest diameter in a cross section of the glass fibers to the shortest diameter in the same cross section of less than 2, preferably less than 1.5, more preferably less than 1.2, even more preferably less than 1.1, most preferably less than 1.05. Of course, one of ordinary skill in the art will appreciate that the aspect ratio, by definition, cannot be less than 1, regardless of the morphology (e.g., round or flat) of the glass fibers.
The optional glass fibers may be round or flat glass fibers selected from the group consisting of: e-glass fibers; a high modulus glass fiber having a tensile modulus of at least 76GPa as measured according to ASTM D2343; and combinations thereof.
When the polyamide composition comprises a glass filler and at least one optional reinforcing agent according to the description above, the combined content of glass filler plus one or more optional reinforcing agents is at least 15wt%, or at least 20wt%, or at least 25wt%, or at least 30wt%, based on the total weight of the polyamide composition. In additional or alternative embodiments, the combined content of glass filler plus one or more optional reinforcing agents is up to 60wt%, or up to 55wt%, or up to 50wt%, based on the total weight of the polyamide composition. In some embodiments, the combined amount of glass filler plus one or more optional reinforcing agents is from 15wt% to 60wt%, or from 20wt% to 60wt%, or from 25wt% to 60wt%, or from 30wt% to 60wt%, or from 20wt% to 55wt%, or from 25wt% to 55wt%, or from 30wt% to 55wt%, or from 20wt% to 50wt%, or from 25wt% to 50wt%, or from 30wt% to 50wt%, based on the total weight of the polyamide composition.
When the polyamide polymer comprises glass filler + one or more optional reinforcing agents, the weight ratio of glass filler based on the combined weight of glass filler + one or more optional reinforcing agents in the polyamide composition is greater than the weight ratio of one or more optional reinforcing agents based on the combined weight of glass filler + one or more optional reinforcing agents in the polyamide composition.
The polyamide composition preferably does not comprise fibrous reinforcing agents.
The polyamide composition preferably does not include glass fibers having an average length of greater than 0.5mm, or greater than 1 mm.
The polyamide composition preferably does not comprise glass spheres (sphere) or spheres (ball), and in particular does not comprise hollow glass spheres.
As described above, the polyamide composition preferably does not include a reinforcing agent other than glass filler.
Optional additives
Optionally, the polyamide composition may further comprise an additive selected from the group consisting of: toughening agents, plasticizers, light stabilizers, ultraviolet ("UV") stabilizers, heat stabilizers, pigments, dyes, antistatic agents, flame retardants, impact modifiers, lubricants, nucleating agents, antioxidants, processing aids, and any combination of two or more thereof.
When the polyamide composition includes one or more optional additives, the total concentration of additives is no more than 15wt%, no more than 10wt%, no more than 5wt%, no more than 3wt%, no more than 2wt%, no more than 1wt%, and/or at least 0.1wt%, or at least 0.2wt%, or at least 0.3wt%.
In particular, the polyamide composition may further comprise at least one impact modifier, heat stabilizer and/or lubricant.
Impact modifiers useful herein are not particularly limited as long as they impart useful properties to the polyamide composition, such as adequate tensile elongation at yield and tensile elongation at break. For example, any rubbery low modulus functionalized polyolefin impact modifier having a glass transition temperature below 0 ℃ is suitable for use in the present invention. Useful impact modifiers include polyolefins, preferably functionalized polyolefins, and in particular elastomers such as SEBS and EPDM.
Useful functionalized polyolefin impact modifiers are available from commercial sources, including maleated polypropylene and ethylene-propylene copolymers (as EXXELOR TM PO available) and a maleic anhydride functionalized ethylene-propylene copolymer rubber containing about 0.6 weight percent pendant succinic anhydride groups, such as from Ekson Mobil chemical company (Exxon Mobil Chemical Company) Rtm.va 1801; as->Acrylate-modified polyethylenes obtainable, e.g. +.>9920, methacrylic acid modified polyethylene from DuPont Company; and->For example->1410 XT, acrylic modified polyethylene from the dow chemical company (Dow Chemical Company); maleic anhydride-modified styrene-ethylene-butylene-styrene (SEBS) block copolymers, e.g.>FG1901 GT or FG 1901X, SEBS that has been grafted with about 2% by weight maleic anhydride, available from Koteng Polymers (Kraton Polymers); maleic anhydride functionalized ethylene-propylene-diene monomer (EPDM) terpolymer rubbers, e.g.>498,1% maleic anhydride functionalized EPDM, available from compton (Crompton Corporation).
Other functionalized impact modifiers that may also be used in the practice of the present invention include ethylene-higher alpha-olefin polymers and ethylene-higher alpha-olefin-diene polymers that possess reactive functionality by grafting or copolymerizing with a suitable reactive carboxylic acid or derivative thereof (such as, for example, acrylic acid, methacrylic acid, maleic anhydride, or esters thereof) and will have a tensile modulus (determined according to ASTM D-638) of up to about 50,000 psi. Suitable higher alpha-olefins include C 3 To C 8 Alpha-olefins such as, for example, propylene, butene-1, hexene-1 and styrene. Alternatively, suitable 1-3 diene monomers may also be polymerizedHydrogenation of homopolymers and copolymers yields copolymers having structures comprising such units. For example, polybutadiene having varying levels of pendant vinyl units can be readily obtained, and these can be hydrogenated to provide ethylene-butene copolymer structures. Similarly, hydrogenation of polyisoprene may be used to provide equivalent ethylene-isobutylene copolymers. Functionalized polyolefins that may be used in the present invention include those having a melt index in the range of from about 0.5 to about 200g/10 min.
In a preferred embodiment, the polyamide composition does not contain an antistatic agent.
Preparation of Polyamide composition
The invention further relates to a process for manufacturing a polyamide composition as detailed above, said process comprising melt blending: the at least one polyamide polymer, the conductive material, the glass filler, one or more optional reinforcing agents other than the glass filler, and any other optional additives (e.g., lubricants, UV stabilizers, heat stabilizers, impact modifiers, etc.).
In the context of the present invention, any melt blending method may be used to mix the polymeric and non-polymeric components.
For example, one or more of the polymeric and non-polymeric ingredients may be fed into a melt mixer (such as a single or twin screw extruder, a stirrer, a single or twin screw kneader, or a Banbury mixer), and the addition step may be one-shot or stepwise addition of all the ingredients in batches. When the one or more polymeric ingredients and the non-polymeric ingredients are added stepwise in batches, a portion of the one or more polymeric ingredients and/or the non-polymeric ingredients is added first and then melt mixed with the remaining one or more polymeric ingredients and non-polymeric ingredients added subsequently until a well-mixed composition is obtained.
If the optional reinforcing agent exhibits a long physical shape (e.g., long or 'continuous' fibers), the reinforcing composition may be prepared using drawing extrusion molding, pultrusion to form long fiber pellets, or pultrusion to form unidirectional composite tapes.
Article and use
Another aspect of the invention provides the use of a polyamide composition in an article.
The polyamide composition may desirably be incorporated into an article, preferably a molded article. Suitable molded articles include electronic device components, particularly mobile electronic device components.
Articles of manufacture notably can be used in mobile electronics, LED packages, electrical and electronic components (including but not limited to power unit components for computing, data systems, and office equipment, and surface mount technology compatible connectors and contacts), medical device components; and electrical protection devices for miniature circuit breakers, contactors, switches and sockets), automotive components, and aerospace components (including but not limited to cabin interior components).
The term "mobile electronic device" is intended to mean an electronic device designed to be convenient for transportation and for use in different locations, in particular an electronic device carried or held by a person. Representative examples of mobile electronic devices may be selected from the group consisting of: mobile electronic telephones, personal digital assistants, notebook computers, tablet computers, radios, cameras and camera accessories, wearable computing devices (e.g., smart watches, smart glasses, etc.), calculators, music players, global positioning system receivers, portable game consoles and host accessories, hard disk drives, and other electronic storage devices. Preferred mobile electronic devices include notebook computers, tablet computers, mobile electronic telephones, and wearable computing devices, such as watches.
The components of the mobile electronic device contemplated herein include, but are not limited to, antenna windows, accessories, snap-in parts, mutually movable parts, functional elements, operating elements, tracking elements, adjustment elements, carrier elements, frame elements, switches, connectors, cables, housings, and any other structural parts other than housings as used in mobile electronic devices, such as speaker parts, for example. In some embodiments, the device component may be a mounting component with mounting holes or other fastening means, including but not limited to a snap-fit connector between itself and another component of the mobile electronic device, including but not limited to a circuit board, microphone, speaker, display, battery, cover, housing, electrical or electronic connector, hinge, radio antenna, camera module, switch, or switch pad (switchpad).
The mobile electronic device may be at least part of an input device.
Particular aspects of the invention relate to a static dissipative component for an electronic device, in particular for a mobile electronic device. Such static dissipative parts may be molded articles comprising or made from the polyamide compositions as described herein.
The mobile electronic device component may also be a mobile electronic device housing. "mobile electronic device housing" refers to one or more of the back cover, front cover, antenna housing, frame, and/or backbone of a mobile electronic device. The housing may be a single article or comprise two or more parts. "backbone" refers to the structural component on which the other components of the device are mounted, such as electronics, microprocessors, screens, keyboards, and keypads, antennas, battery receptacles, etc. The skeleton may be an internal component that is not visible or only partially visible from the exterior of the mobile electronic device. The housing may provide protection for the internal components of the device from impact from environmental factors (e.g., liquids, dust, etc.), as well as contamination and/or damage. Housing components such as covers may also provide substantial or primary structural support as well as impact protection for certain components (e.g., screen and/or antenna) that are exposed to the exterior of the device. The mobile electronic device housing may be selected from the group consisting of: a mobile phone housing, an antenna window, a tablet housing, a notebook housing, a tablet housing, or a watch housing.
The electronic device component may comprise, for example, a radio antenna or a camera module. In this case, the radio antenna may be a WiFi antenna or an RFID antenna. In some such embodiments, at least a portion of the radio antenna is disposed on the polyamide composition. Additionally or alternatively, at least a portion of the radio antenna may be removable from the polyamide composition.
Any description relating to 'mobile' electronic device components applies equally to electronic device components (such as housings, radio antennas or camera modules) that are not 'mobile' (in other words, are part of an electronic device that is carried or held by a person).
Examples of automotive components include, but are not limited to, components in automotive electronics, automotive lighting components (including, but not limited to, motor end caps, sensors, ECU housings, spools and solenoids, connectors, circuit protection/relays, actuator housings, li-ion battery systems, and fuse boxes), traction motors and power electronics (including, but not limited to, battery packs), electrical battery housings.
The article may be molded from the polyamide composition by any method suitable for thermoplastics (e.g., extrusion, injection molding, blow molding, rotational molding, over molding, or compression molding).
Preferred formation of the molded article or (mobile) electronic device component comprises a suitable melt processing method, such as injection molding or extrusion molding of the polyamide composition, injection molding being the preferred molding method.
In some embodiments, the molded article or (mobile) electronic device component according to the invention has at least one of the following characteristics.
The molded article or (mobile) electronic device component according to the invention may have a weight ratio of at least 1.10 +5 Omega cm, or at least 1.5.10 +5 Volume resistivity of Ω·cm. The molded article or (mobile) electronic device component according to the invention may have a weight of at most 5.10 +12 Omega cm, or at most 3.10 +12 Volume resistivity of Ω·cm. In this case, the molded article or (mobile) electronic device component may have a weight ratio of 1.10 +5 Omega cm to 5.10 +12 Volume resistivity of Ω·cm.
The molded article or (mobile) electronic device component according to the invention may have a molding shrinkage (in%) in the transverse direction of at most 0.5%, or at most 0.47%, or at most 0.45%, or at most 0.44%, determined according to ISO 294 (ASTM D955).
The molded article or (mobile) electronic device component according to the invention may have a ratio of mold shrinkage in the flow direction to shrinkage in the transverse direction of greater than 32%, or greater than 35%, or greater than 40%, or greater than 45%, or greater than 50%, or greater than 55%, or greater than 60%, wherein the mold shrinkage in the flow direction and in the transverse direction (in%) is determined according to ISO 294 (ASTM D955).
The molded article or (mobile) electronic device component according to the invention may have a warpage of at most 0.5, or at most 0.4, or at most 0.3, or at most 0.2, or at most 0.18.
Use of polyamide compositions
In some embodiments, the polyamide composition or article may be used to manufacture mobile electronic device components, as described above.
Method for reducing warpage and/or molding shrinkage of polyamide composition
Another aspect of the invention relates to a method for reducing warpage and/or molding shrinkage of a molded article made from a polyamide composition, the method comprising blending a polyamide polymer and a conductive material with a glass filler and optional components to form a molding composition, and then subjecting the molding composition to molding, preferably injection molding, to form the molded article. Blending is preferably performed by melt blending as described above.
Method for reducing the volume resistivity of polyamide compositions
Another aspect of the invention relates to a method for reducing the volume resistivity of a molded article made from a polyamide composition, the method comprising blending a polyamide polymer and a glass filler, and optionally components, with a conductive material to form a molding composition, and then subjecting the molding composition to molding, preferably injection molding, to form the molded article. Blending is preferably performed by melt blending as described above.
Examples
The invention will now be described with reference to the following examples, which are intended to be illustrative only and are not intended to limit the scope of the invention. As used in the examples, "E" represents an example embodiment of the present invention, and "CE" represents a counterexample.
These examples show improved warpage and/or molding shrinkage and CLTE (for dimensional stability), as well as a reduction in volume resistivity of the polyamide composition according to the invention.
Raw materials
The raw materials used to form the samples are provided below:
polyamide 1 ("PA 1"): PA6,10 (tg=50-60 ℃, tm=220 ℃), such as Radipol DC 40 from lanhuqi corporation (Radici)
Polyamide 2 ("PA 2"): PA10T/10I (tg=105 ℃, tm=295 ℃), such as vinyl 6100 from Kingfa corporation (Kingfa)
Glass flakes ("GFla"): MEG160FY-M03 from Nitro Kogyo Co Ltd (NEG)
Glass fiber ("GFib 1") -CSG3PA flat fiber E glass from nitto spinning company (Nittobo)
Glass fiber ("GFib 2") -HM435TM circular S-1 glass from Taishan Co (Taishan)
-conductive material ("CM 1"): APPLY CARBON short CARBON fiber CF.OS.U1-6MM from Procotex, inc
-an optional conductive material ("CM 2"): carbon black concentrate (30wt%Black Pearls800 carbon black, 70wt% pamxd6 as polymer carrier) as0316/0000; a15560; commercially available from Gao Lai Limited (Colloids Limited)
-conductive material ("CM 3"): 15wt% of the catalyst from Hyperion Catalysis InternationalMasterbatch of multiwall carbon nanotubes in the following polymeric carrier: PAMXD6'7003' from mitsubishi gas chemical company (Mitsubishi Gas Chemical co.) '
-guideElectrical material ("CM 4"): 10wt%Masterbatches of NC7000 multiwall carbon nanotubes in the following polymeric carriers: PAMXD6'7003' from mitsubishi gas chemical company (Mitsubishi Gas Chemical co.) '
-conductive material ("CM 5"): 300-micron milled carbon fibers in the form of particles are commercially available as APPLY CARBON CF MLD 300g U1 recycled carbon fiber particles from Procotex corporation; characterized by an average size of about 300.+ -.40 microns, a carbon content of about 94% by weight, a diameter of the monofilament fiber of about 7.+ -.2 microns and 15.10 -3 Average volume resistivity in ohm.m.
-additives: additive package 1 ("AP 1") containing 0.1wt% of a lubricant (calcium stearate Ceasit I from BAEL Luo He Co., baerlocher) and 0.2wt% of a heat stabilizer (from Basf Co., baerlocher) B1171)
-additives: additive package 2 ("AP 2") containing 0.1wt% of a lubricant (calcium stearate Ceasit I from BAR Luo He Co., baerlocher), 0.3wt% of a UV stabilizer (Chimassorb 944LD from Basf) and 0.2wt% of a heat stabilizer (from Basf)B1171)
-optional additives: pigments/dyes may be added to the polyamide composition.
Test method
Tensile Property-ISO 527
The tensile modulus, strength and strain were measured on 5 injection molded ISO 1 a-type tensile samples (total length=170 mm, gauge length=50 mm, test section width=10 mm, and thickness=4 mm)
Notched Izod impact Strength-ASTM D256
The notched Izod impact strength was measured on 5 injection molded rectangular bars having dimensions of 3.2mm thickness by 12.7mm width by 125mm length in J/m.
Notched Izod impact Strength-ASTM D4812
The o unnotched izod impact strength was measured on 5 injection molded rectangular bars having dimensions of 3.2mm thickness by 12.7mm width by 125mm length in J/m.
In some cases, the Izod impact strength characteristics (notched Izod, unnotched Izod) were measured in kJ/m using ISO 180 using 10 injection molded ISO type 1A bars (80+ -2 mm length, 10+ -0.2 mm width, 4+ -0.2 mm thickness) 2 And (5) counting.
·CLTE-ASTM E831
The omicrondimensional change was measured on injection molded samples having dimensions of 3.2mm thickness times 12.7mm width times 12.0 to 13.0mm length. CLTE was measured from 0 ℃ to 50 ℃ using TMA, with a heating rate of 5 ℃/min in the flow and transverse directions.
Molding shrinkage-ISO 294 (ASTM D955)
The °molding shrinkage (molding shrinkage (%) in the flow direction and molding shrinkage (%) in the transverse direction) was measured on 5 injection-molded substrates having dimensions of 60mm width by 60mm length by 2mm thickness.
Warp was determined as follows: the polyamide composition was injection molded into substrates of dimensions 60mm x 2mm according to ASTM D955, as detailed above. The warp is calculated as the percentage of shrinkage in the transverse direction minus the absolute value of the percentage of shrinkage in the flow direction.
Volume resistivity-ASTM D257
The o volume resistivity was measured on 5 injection molded substrates having dimensions of 4 "x 1/8" (length x width x thickness) or 60mm x 2mm (length x width x thickness)
Surface resistivity-ASTM D257
Surface resistivity was measured on 5 injection molded substrates having dimensions of 4 "x 1/8" (length x width x thickness)
Example 1-Polyamide composition with PA6,10
In this example, several polyamide composition samples were prepared in which PA1 (PA 6, 10) was compounded (melt blended) with carbon fiber, optionally carbon black concentrate, additive package 1, and glass flake (GFla).
Samples E1 and E2 contained 44.7wt% PA1, 10wt% carbon fiber and 45wt% glass flakes. Sample E2 further contained 10pph of carbon black concentrate, while sample E1 did not contain any carbon black concentrate.
For comparison, sample CE0 was prepared containing 89.7wt% PA1, 10wt% carbon fiber, but no glass flakes. Samples CE1, CE2 containing 49.7wt% PA1, 50wt% glass flakes and 1 or 10pph carbon black concentrate (but no carbon fiber) were also prepared. Samples CE3 and CE4 contained 44.7wt% of PA1, 50wt% of glass flakes and 1 or 10pph of carbon black concentrate, but 5wt% of carbon fibers, half the content used in samples E1 and E2.
UsingZSK-26 is melt blended with a co-rotating twin screw extruder and the compounded samples are then molded according to ASTM D3641.
Table 1 shows the polyamide composition and also the following properties: the surface and volume resistivity of the composition, mechanical properties including impact properties, CLTE (0 ℃ -50 ℃) properties (ppm in flow direction and transverse direction) and mold shrinkage properties (in% in flow direction and transverse direction).
As shown in table 1, the addition of 10wt% carbon fibers to the polyamide composition in samples E1, E2 reduced the volume resistivity and also the surface resistivity compared to samples CE1 and CE2 without carbon fibers and samples CE3 and CE4 with 5wt% of the same carbon fibers. Samples E1, E2 are static dissipative because their volume resistivity falls at 10 +5 To 5.10 +12 Ohm.cm.
The incorporation of only 10wt% carbon fiber into PA1 also did not reach volume resistivity in the ESD range as seen in sample CE0, compared to samples E1, E2. The production of ESD materials requires a combination of glass flakes (insulating filler) and carbon fibers.
TABLE 1 composition and Properties of samples with PA6,10
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* "pph" means every hundred parts by total weight of PA+GFla+AP1+CM1+CM2 (when present)
And 10wt% of carbon fiber is not containedThe combination of 10wt% carbon fiber and carbon black in the polyamide composition in sample E2 reduced the volume resistivity by 5 orders of magnitude compared to sample E1 of the carbon black concentrate. However, with only 1pph +.>Sample CE1 (without CM 1) of carbon black concentrate compared to CE2 (with 5wt% of CM 1) for a sample with 10pphNo such effect was observed for samples CE2 (without CM 1) and CE4 (with 5wt% of CM 1) of the carbon black concentrate. Thus, if the carbon fibers in the PA 1-based composition are not up to 5.10 +12 If a sufficient amount of volume resistivity of ohm.cm (in the range of ESD volume resistivity) is present, 1-10pph +.>Carbon black concentrates are ineffective for reducing the volume resistivity of PA 1-based compositions to suit ESD.
The addition of 5wt% carbon fiber to the polyamide composition in sample CE3 slightly reduced the volume resistivity, but did not reduce the surface resistivity, compared to sample CE1 without carbon fiber. Regardless, the volume resistivity of sample CE3 remains too high to be within the ESD volume resistivity range.
Furthermore, the samples E1, E2 containing 10wt% carbon fibers have improved elastic modulus and tensile stress at break compared to samples CE3, CE4 containing 5wt% carbon fibers, and are even better than samples CE1, CE2 without carbon fibers.
The samples E1, E2 containing 10wt% of carbon fibers had the same or better tensile elongation at break (%) as the samples CE1, CE2 containing no carbon fibers and the samples CE3, CE4 containing 5wt% of carbon fibers.
Furthermore, for all PA 1-based compositions in table 1, the mold shrinkage characteristics were more isotropic with the addition of glass flakes. The ratio of shrinkage in the flow direction to shrinkage in the transverse direction is from 74% to 82%, very close to isotropic shrinkage. Despite the addition of 10wt% cm1, the transverse molding shrinkage of the polyamide composition in samples E1, E2 remained relatively unchanged compared to samples CE1 to CE4, indicating that the addition of 10wt% cm1 did not adversely affect the transverse molding shrinkage.
When comparing sample E2 with sample E1, sample CE4 with sample CE3, and sample CE2 with sample CE1, the presence of carbon black appears to slightly reduce the transverse molding shrinkage of the PA 1-based composition.
The results obtained with samples E1, E2 demonstrate that by adding more than 5wt% carbon fibers (and optionally carbon black) and 45wt% glass flakes in the PA 1-based composition, a suitable ESD material can be obtained while achieving dimensional stability (maintaining improved molding shrinkage characteristics).
EXAMPLE 2 Polyamide composition with PA10T/10I
In this example, several polyamide composition samples were prepared in which PA2 (PA 10T/10I) was compounded (melt blended) with carbon fiber, optionally carbon black concentrate, additive package 1, and glass flake (GFla).
Samples E3 and E4 contained 44.7wt% PA2, 10wt% carbon fiber and 45wt% glass flakes. Sample E4 further contained 10pph of carbon black concentrate, while sample E3 did not contain any carbon black concentrate.
For comparison, sample CE5 was also prepared containing 49.7wt% PA2, 50wt% glass flakes, and 10pph of carbon black concentrate (but no carbon fiber).
Samples CE6 and CE7 contained 44.7wt% of PA2, 50wt% of glass flakes and 1 or 10pph of carbon black concentrate, but 5wt% of carbon fibers, half the content used in samples E3 and E4.
UsingZSK-26 is melt blended with a co-rotating twin screw extruder and the compounded samples are then molded according to ASTM D3641.
Table 2 shows the polyamide compositions of samples E3, E4, CE5, CE6 and also the following properties: the surface and volume resistivity, mechanical properties, CLTE (0 ℃ to 50 ℃) properties and mold shrinkage properties of the composition.
Reverse example 3-Polyamide composition with PA10T/10I and glass fibers
In this counter example, several samples CE8, CE9 were prepared, wherein PA2 (PA 10T/10I) was compounded (melt blended) with additive package 2 and 30wt% E-glass fiber (GFib 1) or 55wt% S1-glass fiber (GFib 2). These examples are the use of glass fibers to evaluate dimensional instability (by way of mold shrinkage measurements and warp calculations) as compared to glass flakes.
The polyamide composition and properties of samples CE8, CE9 are also provided in table 2.
As shown in table 2, the addition of 10wt% carbon fiber to the polyamide composition in samples E3, E4 reduced the volume resistivity and also the surface resistivity compared to sample CE5 without carbon fiber and samples CE6 and CE7 with 5wt% of the same carbon fiber. Samples E3, E4 were static dissipative because their volume resistivity fell at 10 +5 To 5.10 +12 Ohm.cm. Samples CE5, CE6, and CE7 are not ESD materials.
And 10wt% of carbon fiberThe combination of 10wt% carbon fiber and carbon black in the polyamide composition in sample E4 reduced the volume resistivity by 1 order of magnitude compared to sample E3, which did not contain carbon black. However, this effect was not observed for sample CE7 (5 wt% CM1) with 10pph carbon black concentrate compared to sample CE6 (5 wt% CM1) with only 1pph carbon black concentrate. Thus, if the carbon fibers in the PA 2-based composition are not up to 5.10 +12 The addition of 1-10pph carbon black concentrate is ineffective for reducing the volume resistivity of the PA 2-based composition to be suitable for ESD if present in a sufficient amount of the volume resistivity of ohm. The volume resistivity obtained with samples CE6, CE7 (containing 5wt% cm 1) was still too high to be in the ESD volume resistivity range.
Furthermore, the modulus of elasticity of samples E3, E4 containing 10wt% carbon fibers was improved compared to samples CE6, CE7 containing 5wt% carbon fibers, and even better than sample CE5 without carbon fibers.
In addition, with the addition of glass flakes in samples CE5-CE7 and E3-E4 in Table 2, the molding shrinkage was nearly isotropic. The ratio of the molding shrinkage in the flow direction to the transverse direction ranges from 63% to 78%.
Despite the addition of 10wt% cm1, the transverse molding shrinkage of the polyamide composition in sample E3 remained relatively unchanged compared to samples CE5 to CE7, indicating that the addition of carbon fibers did not adversely affect the transverse molding shrinkage.
TABLE 2 composition and Properties of samples with PA10T/10I
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* "pph" means every hundred parts by total weight of PA+GFla+AP1+CM1+CM2 (when present)
On the other hand, as shown in Table 2, in the case where glass fibers were added to samples CE8 (55 wt% S1-glass fibers) and CE9 (30 wt% E-glass fibers), the molding shrinkage was anisotropic. The ratio of the molding shrinkage in the flow direction to that in the transverse direction was from 13% to 31%, respectively. It was also observed that the warp of samples CE8 (55 wt% S1-glass fibers) and CE9 (30 wt% E-glass fibers) in Table 2 was greater than that observed with the addition of glass flakes in samples CE5-CE7 and E3-E4.
With the results obtained for samples E3, E4, it was demonstrated that by adding more than 5wt% carbon fibers (and optionally carbon black) and 45wt% glass flakes in the PA2 based composition, a suitable ESD material can be obtained, while obtaining dimensional stability (low warpage and improved molding shrinkage characteristics).
Example 4-Polyamide composition with PA6,10
In this example, several polyamide composition samples were prepared in which PA1 (PA 6, 10) was compounded (melt blended) with carbon nanotubes (as master batches "CM3" or "CM 4"), carbon black concentrate "CM2", additive package 1, and glass flakes (GFla). UsingZSK-26 is melt blended with a co-rotating twin screw extruder and the compounded samples are then molded according to ASTM D3641.
Samples E5 and E6 contained two different amounts of carbon nanotube masterbatch "CM3" as the conductive material, resulting in actual weight contents of 2.25wt% and 3wt% CNT, respectively. Samples E7 and E8 contained two different amounts of carbon nanotube masterbatch "CM4" as the conductive material, resulting in actual weight content in PAMXD6 as the polymer carrier of 1.5wt% and 2wt% CNT, respectively.
For comparison, sample CE10 without carbon nanotubes was prepared.
Table 3 shows the polyamide composition and also the following properties: the surface and volume resistivity of the composition, mechanical properties including impact properties, CLTE (0 ℃ -50 ℃) properties (ppm in flow direction and transverse direction) and mold shrinkage properties (in% in flow direction and transverse direction).
TABLE 3 composition and Properties of samples with PA6,10
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* "pph" means per hundred parts by total weight of PA+GFla+AP1+CDM2+CDM3 or CM4
As shown in table 3, the addition of from 1.5wt% to 3wt% carbon nanotubes (MWCNT) to the polyamide composition in samples E5-E8 reduced the volume resistivity and also the surface resistivity compared to sample CE10 without carbon nanotubes. Samples E5-E8 were static dissipative because their volume resistivity fell at 10 +5 To 5.10 +12 Ohm.cm. Sample CE10 is not an ESD material.
Although not shown, the addition of less than 1wt% carbon nanotubes (MWCNTs) to the polyamide composition does not reduce the volume resistivity below a maximum of 5.10 +12 Ohm.cm value to provide ESD material.
To obtain 10 +5 The minimum volume resistivity of ohm.cm to provide an ESD material, the wt% of carbon nanotubes added to the polyamide composition can be increased to higher than 3wt% cnt content (used in sample E6), e.g., up to 5wt% cnt or up to 6wt% cnt, to reduce the volume resistivity by at least about 2 orders of magnitude.
With the results obtained for samples E5-E8, it was demonstrated that by adding from 1.5 to 3wt% carbon nanotubes and 50wt% glass flakes to the PA1 based composition, a suitable ESD material can be obtained, while achieving dimensional stability (low warpage and improved mold shrinkage characteristics).
EXAMPLE 5 Polyamide composition with PA10T/10I
In this example, sample E9 of the polyamide composition was prepared in which PA2 (PA 10T/10I) was compounded (melt blended) with 10wt% of milled carbon fiber particles ("CM 5") as a conductive material, carbon black concentrate "CM2", additive package 1, and glass flake (GFla). UsingZSK-26 is melt blended with a co-rotating twin screw extruder and the compounded samples are then molded according to ASTM D3641. />
For comparison, sample CE11 without milled carbon fiber was prepared.
The polyamide compositions and properties of samples CE11 and E9 are provided in table 4.
As shown in table 4, the addition of 10wt% of milled carbon fiber (in particulate form) to the polyamide composition in sample E9 significantly reduced the volume resistivity by 10 orders of magnitude compared to sample CE11 without milled carbon fiber. Sample E9 was static dissipative because its volume resistivity fell at 10 +5 To 5.10 +12 Ohm.cm. Sample CE11 is not an ESD material.
TABLE 4 composition and Properties of samples with PA10T/10I
* "pph" means every hundred parts by total weight of PA+GFla+AP1+CM2+CM5
In addition, the sample E9 having 10wt% milled carbon fiber has an improved tensile modulus of elasticity and tensile strength compared to the sample CE11 having no milled carbon fiber. Likewise, the notched Izod impact properties are improved with the addition of milled carbon fibers.
Furthermore, the addition of 10wt% of milled carbon fiber does not adversely affect the molding shrinkage and warpage; conversely, it improves the molding shrinkage and warpage. The transverse molding shrinkage (0.3%) was greatly improved in sample E9 compared to sample CE11 (0.43%). The ratio of the molding shrinkage in the flow direction to the transverse direction was 90% compared to 70% in sample CE11, and the estimated warp value was reduced from 0.13 (CE 11) to 0.03 (E9). With the addition of 10wt% milled carbon fiber in sample E9, the mold shrinkage was nearly isotropic.
With the results obtained in sample E9, it was demonstrated that by adding from 10wt% of milled carbon fiber particles and 50wt% of glass flakes in the PA2 based composition, a suitable ESD material can be obtained while achieving dimensional stability (low warpage and improved mold shrinkage characteristics) and maintaining excellent mechanical properties.
While the preferred embodiments of the present invention have been shown and described, modifications thereof can be made by one skilled in the art without departing from the spirit or teaching of the invention. The embodiments described herein are exemplary only and are not limiting. Many variations and modifications of the composition, article, and method are possible and are within the scope of the invention. The scope of protection is therefore not limited by the description set out above, but is only limited by the claims which follow, that scope including all equivalents of the subject matter of the claims. Each of the claims is incorporated into this specification as an embodiment of the invention. Thus, the claims are a further description and are an addition to the preferred embodiments of the present invention. The incorporation of any reference by reference of documents above is limited such that no subject matter is incorporated that is contrary to the explicit disclosure herein.
The disclosures of all patent applications and publications cited herein are hereby incorporated by reference to the extent that they provide exemplary, procedural or other details supplementary to those set forth herein. The disclosure of any patent, patent application, and publication incorporated herein by reference should be given priority to the description of the application to the extent that it may result in the terminology being unclear.
Claims (15)
1. A polyamide composition comprising:
at least 20 weight percent (wt%) of a polyamide polymer,
from greater than 1wt% and up to 20wt% of a conductive material comprising carbon fibers, carbon nanotubes, or any combination thereof, and
from 20 to 60% by weight of a glass filler having a three-dimensional structure characterized by an average length of at most 500 micrometers, said glass filler comprising at least 20% by weight of glass flakes,
wherein the wt% is based on the total weight of the polyamide composition.
2. The polyamide composition of claim 1, wherein the polyamide polymer comprises a semiaromatic polyamide, preferably polyphthalamide.
3. The polyamide composition of claim 1 or 2, wherein the polyamide polymer comprises a semiaromatic polyamide selected from the group consisting of: PA10T/10I; PA10T; PA6T/6I; PA6T; PA9T; PA12T; PA10T/66; PA6T/66; PA6, I; PA12I; PAMXD6; PAPXD10; and any combination thereof.
4. The polyamide composition of claim 1, wherein the polyamide polymer comprises an aliphatic polyamide selected from the group consisting of: PA610; PA612; PA10/10; PA12; PA510; PA66; PA10/12; and any combination thereof.
5. The polyamide composition of any one of claims 1 to 4 wherein the glass filler further comprises chopped round or flat glass fibers.
6. The polyamide composition of any one of claims 1 to 5 wherein the glass filler comprises from 30 to 55wt% glass flakes based on the total weight of the polyamide composition.
7. The polyamide composition of any one of claims 1 to 6, wherein the electrically conductive material comprises chopped carbon fibers, milled/chopped carbon fibers in particles, single-walled carbon nanotubes (SWCNTs), double-walled carbon nanotubes (DWCNTs), multi-walled carbon nanotubes (MWCNTs), or any combination thereof.
8. The polyamide composition of any one of claims 1 to 7, wherein the conductive material further comprises carbon black powder.
9. The polyamide composition of any one of claims 1 to 8, wherein the conductive material further comprises a carbon-based three-dimensional structure selected from the group consisting of: flakes, powders, microspheres, nanoparticles, nanofibers, nanoflakes, nanoropes, nanoribbons, nanofibrils, nanoneedles, nanoplatelets, nanorods, carbon nanocones, carbon nanorolls, nanoplatelets, nanodots, dendrites, discs, or any other three-dimensional body, alone or in combination.
10. The polyamide composition of any one of claims 1 to 9 wherein the electrically conductive material has a weight ratio of less than 2-10 measured according to ASTM D257 -2 Omega cm, or at most 1.10 -2 Omega cm, or at most 5.10 -3 Omega cm, or at most 3.10 -3 Omega cm, or at most 1.10 -3 Volume resistivity of Ω. cm, preferably from 1.10 measured according to ASTM D257 -4 Omega cm to 20.10 -4 Volume resistivity of Ω·cm.
11. The polyamide composition of any one of claims 1 to 10, which is static dissipative.
12. A process for making the polyamide composition of any one of claims 1 to 11, the process comprising melt blending the polyamide polymer, the conductive material, the glass filler, and any optional additives selected from the group consisting of: another reinforcing agent, toughening agent, plasticizer, light stabilizer, ultraviolet stabilizer, heat stabilizer, pigment, dye, antistatic agent, flame retardant, impact modifier, lubricant, nucleating agent, antioxidant, processing aid, and any combination of two or more thereof, different from the glass filler.
13. A molded article comprising the polyamide composition of any one of claims 1 to 11.
14. A mobile electronic device component comprising the polyamide composition of any one of claims 1 to 11.
15. The molded article of claim 13 or the mobile electronic device component of claim 14 having at least one of the following characteristics:
from 1.10 as measured according to ASTM D257 +5 Omega cm to 5.10 +12 Volume resistivity of Ω. cm;
-a ratio of mold shrinkage in the flow direction to mold shrinkage in the transverse direction of greater than 32%, or greater than 35%, or greater than 40%, or greater than 45%, or greater than 50%, or greater than 55%, or greater than 60%, wherein the mold shrinkage in the flow direction and in the transverse direction (in%) is determined according to ISO 294 (ASTM D955);
-a warp of at most 0.5, or at most 0.4, or at most 0.3, or at most 0.2, or at most 0.18, and/or
Up to 0.5%, or up to 0.47%, or up to 0.45%, or up to 0.44% of the molding shrinkage (in%) in the transverse direction, determined according to ISO 294 (ASTM D955).
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| US202163171216P | 2021-04-06 | 2021-04-06 | |
| US63/171216 | 2021-04-06 | ||
| EP21189881.2 | 2021-08-05 | ||
| PCT/EP2022/058900 WO2022214438A1 (en) | 2021-04-06 | 2022-04-04 | Electrostatic dissipative polyamide composition and article comprising it |
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| CN117120365A true CN117120365A (en) | 2023-11-24 |
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